Froth flotation process with branched polyalkylenepolyamines



United States Patent 6 Claims. (Cl. 209-166) This application is adivision of our application Ser. No. 47,386, filed August 4, 1960, nowUS. Patent No. 3,200,106, gnanted on August 10, 1965.

This invention relates to branched polyalkylene polyamines and toderivatives thereof. More particularly, this invention relates to saidbranched po-lyamines and to branched polyamine derivatives containingvarious groups, such as the oxyalkylated, acylated, alkylated,carbonylated, olefinated, etc., derivatives thereof, prepared byintroducing such groups individually, alternately, in combination, etc.,including for example, derivatives prepared by varying the order ofadding such groups, by increasing the number and order of adding suchgroups, and the like.

This invention also relates to methods of using these products, whichhave an unexpectedly broad spectrum of uses, for example, asdemulsifiers for water-in-oil emulsions; as demulsifiers foroil-in-water emulsions; as corrosion inhibitors; as fuel oil additivesfor gasoline, diesel fuel, jet fuel, and the like; as lubricating oiladditives; as scale preventatives; as chelating agents or to formchelates which are themselves useful, for example, as antioxidants,gasoline stabilizers, fungicides, etc.; as flotation agents, forexample, as flotation collection agents; as asphalt additives oranti-stripping agents for asphaltrnineral aggregate compositions; asadditives for compositions useful in acidizing calcareous rstra tas ofoil wells; as additives for treating water used in the secondaryrecovery of oil and in disposal wells; as additives used in treatingoil-well strata in primary oil recovery to enhance the flow of oil; asemulsifiers for both oil-inwater and water-in-oil emulsions; asadditives for slushing oils; as additives for cutting oils; as additivesfor oil to prevent emulsification during transport; as additives fordrilling muds; as agents useful in removing mud sheaths from new-1ydrilled wells; as dehazing or foginhibiting agents for fuels; asadditives for preparing sand or mineral slurries useful in treating oilWells to enhance the recovery of oil; as agents for producing polymericemulsions useful in preparing water-vapor impermeable paper board; asagents in paraffin solvents; as agents in preparing thickened silicaaerogel lubricants; as gasoline additives to remove copper therefrom; asdeicing and antistalling agents for gasoline; as antiseptic,preservative, bactericidal, bacteriostatic, germicidal, fungicidalagents; as agents for the textile industry, for example, as meroerizingassistants, as wetting agents, as rewet-ting agents, as dispersingagents, as detergents, as penetrating agents, as softening agents, asdyeing assistants, as anti-static agents, and the like; as additives forrubber latices; as entraining agents for concrete and cements; asanti-static agents for rugs, floors, upholstery, plastic and waxpolishes, textiles, etc.; as detergents useful in metal cleaners, infloor oils, in dry cleaning, in general cleaning, and the like; asagents useful in leather processes such as in fiat liquoring, pickling,acid degreasing, dye fixing, and the like; as agents in metal pickling;=as additives in paints for improved adhesion of primers, in preventingwater-spotting in lacquer; as antiskinners for pigment flushing,grinding and dispersing, as antifeathering agents in ink; as agents inthe preparation of wood pulp and pulp slurries, as emulsifiers forinsecticidal compositions and agricultural sprays such as DDT, 24-D(Toxaphene), chlordane, nicotine sulfate, hexachloracyclohexane, and thelike; as agents useful in building materials, for example, in the waterrepellent treatment of plaster, concrete, cement, roofing materials,floor sealers; as additives in bonding agents for various insulatingbuilding materials; and the like.

THE BRANCHED POLYAMINE The branched polyamines employed herein arepolyalkylene polyamines wherein the branched group is a side chaincontaining on the average at least one nitrogen-bonded aminoalkylenei.e.

r '1 H R R L group per nine amino units present on the main chain, forexample, 1-4 of such branched chains per nine units on the main chain,but preferably one side chain unit per nine main chain units. Thus,these polyamines contain at least three primary amino groups and atleast one tertiary amino group.

These reagents may be expressed by the formula:

where n is an integer, for example, 1-20 or more but preferably 1-3,wherein R is preferably ethylene, but may be propylene, butylene, etc.(straight chained or branched).

The preferred embodiments are presented by the following formula:

3 4 The radicals in the brackets may be joined in a head- 1-2 hours orlonger, one can in many cases recover a to-head or a head-to-tailfashion.- Compounds described second mole of water for each mole ofcarboxylic acid by this formula wherein n: l-3 are manufactured andgroup employed, the first mole of water being evolved dursold asPolyamines N-400, N-800, N-1200 etc. Polying amidification. The productformed in such cases conamine N-400 has the above formula wherein 21:1.5 tains a cyclic amidine ring, such as an imidazoline or These compoundsmay be prepared by a wide variety a tetrahydropyrimidine ring. Infraredanalysis is a conof methods. One method comprises the reaction ofethvenient method of determining the presence of these anolamine andammonia under pressure over a fixed bed groups.

of a metal hydrogenation catalyst. By controlling the Water is formed asa by-product of the reaction beconditions of this reaction one mayobtain varying tween the acylating agent and the branched polyamineamounts of piperazine and polyamines as well as the reactant. In orderto facilitate the removal of this water, branched chain polyalkylenepolyamine useful in this into effect a more complete reaction inaccordance with vention. This process is described in Australianapplicathe principle of Le Chatelier, a hydrocarbon solvent which tionNo. 42,189, now Australian Patent No. 233,766, forms an azeotropicmixture with water can be added and in the German Patent No. 14,480(March 17, 1958) to the reaction mixture. Heating is continued with thereported in Chem. Abstracts, August 10, 1949, 14,129. liquid reactionmixture at the preferred reaction tem- These branched polyamines canalso be prepared by perature, until the removal of water by azeotropicdistilthe following reactions: lation has substantially ceased. Ingeneral, any hydroll H R0011 H 11 H CHr-CH: NHs-CHaCHnN-CHnCHzNH:IIICHaCH2N-CH:CHi I H H S0201 H H 'Irlethylene tetramlneNCH:CHsN-CHaCHr-N NCHaCHzNCHzCH:-N I I I I followed by hydrolysis o= 1CIH; 0:0 0:0 113, 0:0 R (IEH: Ii I l CH2 fl 0H 1 H H H HHgNCHzCHzN-OH2CHr-NCHaCHr-N-CHCH-N-CHaCHzN-CHzCHzIII-CHzCHaNH: CH: (1H1I HI CH2 NE: I NH,

Variations on the above procedure can produce other carbon solvent whichforms an azeotropic mixture with branched polyamines. 40 Water can beused. It is preferred, however, to use an The branched nature of thepolyamine imparts unusual aromatic hydrocarbon solvent of the benzeneseries. Nonproperties to the polyamine and its derivatives. limitingexamples of the preferred solvent are benzene, For the sake of brevityand to simplify presentation, toluene, and xylene. The amount of solventused is a the invention will be described by the selection of onevariable and non-critical factor. It is dependent on the branchedpolyamine to illustrate the reactions and uses size of the reactionvessel and the reaction temperature thereof (i.e. N-400). However, it isto be understood selected. Accordingly, a sufficient amount of solventmust that such presentation is purely for illustration and the be usedto support the azeotropic distillation, but a large invention should notbe limited thereto. excess must be avoided since the reactiontemperature will be lowered thereby. Water produced by the reactionACYLATION can also be removed by operating under reduced pressure. Awide variety of acylating agents can be employed. When operating with areaction vessel equipped with a Acylation is carried out underdehydrating condition, i.e., reflux condenser provided with a watertakeoff trap, water is removed. Any of the well-known methods ofsufficient reduced pressure can be achieved by applying acylation can beemployed. For example, heat alone, a slight vacuum to the upper end ofthe condenser. The heat and reduced pressure, heat in combination withan pressure inside the system is usually reduced to between azeotropingagent, etc., are all satisfactory. about 50 and about 300 millimeters.If desired, the water The temperature at which the reaction between thecan be removed also by distillation, while operating under acylatingagent and the branched polyalkylenepolyamine relatively high temperatureconditions. is effected is not too critical a factor. Since thereactions The time of reaction between the acylating agent and involvedappear to be an amide-formation reaction and the branched polyaminereactant is dependent on the a condensation reaction, the generaltemperature condiweight of the charge, the reaction temperatureselected, tions for such reactions, which are well known to those andthe means employed for removing the water from skilled in the art, areapplicable. the reaction mixture. In practice, the reaction is con-Acylation is conducted at a temperature sufficiently tinued until theformation of Water has substantially high to eliminate water and belowthe pyrolytic point ceased. In general, the time of reaction will varybetween of the reactants and the reaction products. In general, about 4hours and about ten hours. the reaction is carried out at a temperatureof from 120 Although a wide variety of carboxylic acids produce to 280C., but preferably at 140 to 200 C. excellent products, carboxylic acidshaving more than 6 The product formed on acylation will vary with thecarbon atoms and less than 40 carbon atoms but preferparticularconditions employed. First the salt, then ably 8-30 carbon atoms givemost advantageous products. the amide is formed. If, however, afterforming the The most common examples include the detergent formamide ata temperature between 140-250 C., but usually ing acids, i.e., thoseacids which combine with alkalies not above 200 C., one heats suchproducts at a higher to produce soap or soap-like bodies. Thedetergentrange, approximately 250-280 C., or higher, possibly up formingacids, in turn, include naturally-occurring fatty to 300 C. for asuitable period of time, for example, acids, resin acids, such asabietic acid, naturally occurring petroleum acids, such as naphthenicacids, and carboxy acids, produced by the oxidation of petroleum. Aswill be subsequently indicated, there are other acids which havesomewhat similar characteristics and are derived from somewhat differentsources and are diiferent in structure, but can be included in the broadgeneric term previously indicated.

Suitable acids include straight chain and branched chain, saturated andunsaturated, aliphatic, alicyclic, fatty, aromatic, hydroaromatic, andaralkyl acids, etc.

Examples of saturated aliphatic monocarboxylic acids are acetic,proprionic, butyric, valeric, caproic, heptanoic, caprylic, nonanoic,capric, undecanoic, lauric, tridecanoic, myriatic, pentadecanoic,palmitic, heptadecanoic, stearic, nonadecanoic, eicosanoic,heneicosanoic, docosanoic, tricosanoic, tetracosanoic, pentacosanoic,cerotic, heptacosanoic, montanic, nonacosanoic, melissic and the like.

Examples of ethylenic unsaturated aliphatic acids are acrylic,methacrylic, crotonic, anglic, teglic, the pentenoic acids, the hexenoicacids, for example, hydrosonbic acid, the heptenoic acids, the octenoicacids, the nonenoic acids, the decenoic acids, for example, obtusilicacid, the undecenoic acids, the dodecenoic acids, for example,lauroleic, linderic, etc., the tridecenoic acids, the tetradecenoicacids, for example, myristoleic acid, the pentadecenoic acids, thehexadecenoic acids, for example, palmitoleic acid, the heptadecenoicacids, the octodecenoic acids, for example, petrosilenic acid, oleicacid, elardic acid, the nouadecenoic acids, for example, the eicosenoicacids, the docosenoic acids, for example, erucic acid, brassidic acid,cetoleic acid, the tetradosenic acids, and the like.

Examples of dienoic acids are the pentadienoic acids, the hexadienoicacids, for example, sorbic acid, the octadienoic acids, for example,linoleic, and the like.

Examples of the trienoic acids are the octadecatrienoic acids, forexample, linolenic acid, eleostearic acid, pseudoeleostearic acid, andthe like.

Carboxylic acids containing functional groups such as hydroxy groups canbe employed. Hydroxy acids, particularly the alpha hydroxy acids includeglycolic acid, lactic acid, the hydroxyvaleric acids, the hydroxycaproic acids, the hydroxyheptanoic acids, the hydroxy caprylic acids,the hydroxynonanoic acids, the hydroxycapric acids, the hydroxydecanoicacids, the hydroxy lauric acids, the hydroxy tridecanoic acids, thehydroxymyr-istic acids, the hydroxypentadecanoic acids, thehydroxypalmitic acids, the hydroxyhexadecanoic acids, thehydroxyheptadecanoic acids, the hydroxy stearic acids, thehydroxyoctadecenoic acids, for example, ricinoleic acid, ricinelardicacid, hydroxyoctadecyno-ic acids, for example, ricinstearolic acid, thehydroxyeicosanoic acids, for example, hydroxyar-achidic acid, thehydroxydocosanoic acids, for example, hydroxybehenic acid, and the like.

Examples of acetylated hydroxyacids are ricinoleyl lactic acid, acetylricinoleic acid, chloroacetyl ricinoleic acid, and the like.

Examples of the cyclic aliphatic carboxylic acids are those found inpetroleum called naphthenic acids, hydrocarbic and chaumoogric acids,cyclopentane carboxylic acids, cyclohexanecanboxylic acid, campholicacid, :Eenchlolic acids, and the like.

Examples of aromatic monocanboxylic acids are benzoic acid, substitutedbenzoic acids, for example, the toluic acids, the xyleneic acids, alkoxybenzoic acid, phenyl benzoic acid, naphthalene carboxylic acid, and thelike.

Mixed higher fatty acids derived from animal or vegeta'ble sources, forexample, lard, cocoanut oil, rapeseed oil, sesame oil, palm kernel oil,palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow,soyabean oil, peanut oil, castor oil, seal oils, whale oil, shark oil,and other fish oils, teaseed oil, partially or completely hydrogenatedanimal and vegetable oils are advantageously employed.

Fatty and similar acids include those derived from various waxes, suchas beeswax, spermaceti, montan wax, Japan wax, coccerin and carnaubawax. Such acids include carnaubic acid, cerotic acid, lacceric acid,montanic acid, psyllas-tearic acid, etc. One may also employ highermolecular weight carboxylic acids derived by oxidation and othermethods, such as from paratlin wax, petroleum and similar hydrocarbons;resinic and hydroaromatic acids, such as hexahydrobenzoic acid,hydrogenated naphthoic, hydrogenated carboxy diphenyl, naphthenic, andabietic acid; Twitchell fatty acids, carboxydiphenyl pyridine carboxylicacid, blown oils, blown oil fatty acids and the like.

Other suitable acids include phenylstearic acid, benzoylnonylic acid,cetyloxybutyric acid, cetyloxyacetic acid, chlorstearic acid, etc.

Examples of the polycarboxylic acids are those of the aliphatic series,for example, oxalic, malonic, succinic, glutaric, adipic, pimelic,suberic, azelaic, sebacic, nonanedicarboxylic acid, decanedicarboxylicacids, undecanedicarboxylic acids, and the like.

Examples of unsaturated aliphatic polycarboxylic acids are fumaric,maleic, mesocenic, citraconic, glutonic, itaconic, muconic, aconiticacids, and the like.

Examples of aromatic polycarboxylic acids are phth-alic, isophthalicacids, terephthalic acids, substituted derivatives thereof (e.g. alkyl,chloro, alkoxy, etc., derivatives), biphenyld-icarboxylic acid,dipheuylether dicarboxylic acids, diphenylsulfone dicarboxylic acids andthe like.

Higher aromatic polycarboxylic acids containing more than two carboxylicgroups are himimellitic, trimellitic, trimesic, mellophanic, prehnitic,pyromellitic acids, mellitic acid, and the like.

Other polycarboxylic acids are the dimeric, trimeric, and polymericacids, for example, dilinoleic, trilino-leic, and] other polyacids soldby Emery Industries, and the like. Other polycanboxylic acids includethose containing ether groups, for example, diglycolic acid. Mixtures ofthe above acids can be advantageously employed.

In addition, acid precursors such as acid anhydrides, esters, acidhalides, glycerides, etc., can be employed in place of the free acid.

Examples of acid anhydrides are the alkenyl succinic acid anhydrides.

Any alkenyl succinic acid anhydride or the corresponding acid isutilizable [for the production of the reaction products of the presentinvention. The general structural formulae of these compounds are:

Anhydride C Hr-O Acid limit to the number of carbon atoms therein.However, it is preferred to use an alkenyl succinic acid anhydridereactant having between about 8 and about 18 carbon atoms per alkenylradical. Although their use is less desirable, the alkenyl succinicacids also react, in accordance with this invention, to producesatisfactory reaction products. It has been found, however, that theiruse necessitates the removal of water formed during the reaction andalso often causes undesirable side reactions to occur to some extent.Nevertheless, the alkenyl succinic acid anhydrides and the alkenylsuccinic acids are interchangeable for the purposes of the presentinvention. Accordingly, when the term alkenyl succinic acid anhydride,is used herein, it must be clearly understood that it embraces thealkenyl succinic acids as well as their anhydrides, and the derivativesthereof in which the olefinic double bond has been saturated as setforth hereinbefore. Non-limiting examples of the alkenyl succinic acidanhydride reactant are ethenyl succinic acid anhydrides; ethenylsuccinic acid; ethyl succinic acid anhydride; propenyl succinic acidanhydride; sulfurized propenyl succinic acid anhydride; butenyl succinicacid; Z-methylbutenyl succinic acid anhydride; 1,2-dichloropentylsuccinic acid anhydride; hexenyl succinic acid anhydride; hexyl succinicacid; sulfurized 3-methylpentenyl succinic acid anhydride;2,3-dimethylbutenyl succinic acid anhydride; 3,3-dimethylbutenylsuccinic acid; 1,2-dibromo-2-ethylbutyl succinic acid; heptenyl succinicacid anhydride; 1,2-diiodooctyl succinic acid; octenyl succinic acidanhydride; Z-methyl-heptenyl succinic acid anhydride; 4-ethylhexenylsuccinic acid; 2-isopropylpentenyl succinic acid anhydride; nonenylsuccinic acid anhydride; 2-propylhexenyl succinic acid anhydride;decenyl succinic acid; decenyl succinic acid anhydride;5-methyl-2-isopropylhexenyl succinic acid anhydride;1,2-dibromo-2-ethyloctenyl succinic acid anhydride; decyl succinic acidanhydride; undecenyl succinic acid anhydride; 1,2-dichloroundecylsuccinic acid anhydride; 1,2-dichloro-undecyl succinic acid;3-ethyl-2-t-butylpentenyl succinic acid anhydride; dodecenyl succinicacid anhydride; dodecenyl succinic acid; 2-propylnonenyl succinic acidanhydride; 3-butyloctenyl succinic acid anhydride; tridecenyl succinicacid anhydride; tetradecenyl succinic acid anhydride; hexadecenylsuccinic acid anhydride; sulfurized octadecenyl succinic acid; octadecylsuccinic acid anhydride; 1,2-dibromo-Z-methylpentadecenyl succinic acidanhydride; 8-propylpentadecyl succinic acid anhydride; eicosenylsuccinic acid anhydride; l,2-dichloro-2-methylnonadecenyl succinic acidanhydride; 2-octyldodecenyl uccinic acid; 1,2-diiodotetracosenylsuccinic acid anhydride; hexacosenyl succinic acid; hexacosenyl succinicacid anhydride; and hentriacontenyl succinic acid anhydride.

The methods of preparing the alkenyl succinic acid anhydrides are wellknown to those familiar with the art. The most feasible method is by thereaction of an olefin with maleic acid anhydride. Since relatively pureolefins are difficult to obtain, and when thus obtainable, are often tooexpensive for commercial use, alkenyl succinic acid anhydrides areusually prepared as mixtures by reacting mixtures of olefins with maleicacid anhydride. Such mixtures, as well as relatively pure anhydrides,are utilizable herein.

In summary, without any intent of limiting the scope of the invention,acylation includes amidification, the formation of the cyclic amidinering, the formation of acid imides such as might occur when anhydridessuch as the alkenylsuccinic acids are reacted, i.e.,

R-CH-C wherein P=branched polyamine residue, polymers as might occurwhen a dicarboxylic acid is reacted intermolecularly with the branchedpolyamine, cyclization as might occur when a dicarboxylic acid reactsintramolecularly with the polyamine as contrasted to intermolecularreactions, etc. The reaction products may contain other substances.Accordingly, these reaction products are most accurately defined by adefinition comprising a recitation of the process by which they areproduced, i.e., by acylation.

The moles of acylating agent reacted with the branched polyamine willdepend on the number of acylation reactive positions contained thereinas well as the number of moles of acylating agent one wishes toincorporate into the molecule. We have advantageously reacted 1 to 10moles of acylating agent per mole of Polyamine N-400, but preferably 1to 6 moles. With Polyamine N-800 and N-1200, twice and three times asmany moles of acylating agent can be employed respectively, i.e. withPolyamine N-800, 1-20 moles, preferably 1-12; with N-1200, 1-30, butpreferably l-18. Optimum acylation will depend on the particularapplication.

The following examples are illustrative of the preparation of theacylated branched polyamines.

The following general procedure is employed in acylating. The branchedpolyamine is mixed with the desired ratio of acid and a suitableazeotroping agent is added. Heat is then applied. After the removal ofthe calculated amount of water (1 to 2 equivalents per carboxylic acidgroup of the acid employed), heating is stopped and the azeotropingagent is evaporated under vacuum. The temperature during the reactioncan vary from to 200 C. Where the formation of the cyclic amidine typestructure is desired the maximum temperature is generally ISO-250 C. andmore than one mole of Water per carboxy lic group is removed. Thereaction times range from 4 to 24 hours. Here again, the true test ofthe degree of reaction is the amount of water removed.

Example 3-A In a 5 liter, 3 necked flask furnished with a stirringdevice, thermometer, phase separating trap, condenser and heatingmantle, 1 mole (400 grams) of Polyamine N-400 is dissolved in an equalWeight of xylene, i.e., 400 grams. 845 grams of oleic acid (3 moles) isadded to the polyamine with stirring in about ten minutes. The reactionmixture is then heated gradually to about C. in half an hour and thenheld at about C. over a period of 3 hours until 54 grams (3 moles) ofWater is collected in the side of the tube. The solvent is then removedwith gentle heating under reduced pressure of approximately 20 mm. Theproduct is a dark, viscous, xylene-soluble liquid.

Example 3A The prior example is repeated except that the final reactiontemperature is maintained at 240 C. and 90 grams (5 moles) of water areremoved instead of 54 grams (3 moles). Infrared analysis of the productindicates the presence of a cyclic amidine ring.

The following examples of acylated branched polyamines are prepared inthe manner of the above examples from Polyamine N-400 by employing 400grams of polyamine in each example. The products obtained are dark,viscous materials.

In the examples the symbol A identified the acylated branched polyamine.Thus, specifically 1-A, represents acylated Polyamine N-400, whichpolyamine is employed in all the reactions of the following table.

TABLE I.--ACYLATED PRODUCTS OF POLYAMINE N400 Acid Moles of WaterRemoved Ex. Acid/Mole oi Polyamine Name Grams N-400 Moles Grams 1-A1-..Acetic (60) 540 9:1 10.1 182 1As... do 400 8:1 10.1 182 7:1 9. 2 166 5:17. 1 128 3: 1 5. 3 95 1:1 2. 36 :1 7. 2 129 4:1 6.0 108 3:1 5.1 92 6:15. 9 106 3: 1 3. 0 54 3:1 5.0 90 4:1 5. 9 106 3:1 3. 2 58 1:1 1. 1 203:1 3.0 54 2:1 2. 2 40 3:1 5. 3 95 2: 1 3. 0 54 4:1 6. 2 112 3:1 4. 5 810. 5:1 1. 9 35 0.66:1 4.1 74 do 3:1 6. 3 113 Allrenyl (C12) Suc- 1 0644:1 6.1 111 (311110. Anhydride (266) 798 3:1 3. 2 58 d0 532 2:1 0.3 5.4

Alkenyl (Om) suo- 966 3:1 5. 2 94 cinic.

644 2:1 2.1 38 644 2: 1 0. 2 3. 6 858 3:1 5.0 90 286 1:1 1. 2 22 460 0.5:1 1. 1 20 920 1:1 1. 2 22 610 5:1 4.7 85 366 3:1 31 56 244 2:1 2. 3 41134 1:1 1. 0 18 107. 2 0. 8:1 0.8 14 d0 67 05:1 0.5 9 anhydride 98 1:10. 2 36 15A2 do 78. 4 0. 8:1 0. 0 15-11 do 49 0. 5:1 0.1 1.8 16A1Naphthenic (330) 990 3:1 3 54 3Sunaptic Acid 17-11 Terephthalie (166)-332 2:1 4 72 17A d0 498 3:1 5 90 17-113--. do 830 5:1 6 108 *Chieisubstituent of oiticica oil is the glyceride of licanic acid:

The following table presents specific illustration of compounds otherthan N-400 and its derivatives.

TABLE IA.-ACYLATED PRODUCTS 1 0 OXYALKYLATION These branched polyaminescan be oxyalkylated in the conventional manner, for example, by means ofan alpha-beta alkylene oxide such as ethylene oxide, propylene oxide,butylene oxide, octylene oxide, a higher alkylene oxide, styrene oxide,glycide, methylglycide, etc., or combinations thereof. Depending on theparticular application desired, one may combine a large proportion ofalkylene oxide, particularly ethylene oxide, propylene oxide, acombination or alternate additions or propylene oxide and ethyleneoxide, or smaller proportions thereof in relation to the branchedpolyamine. Thus, the molar ratio of alkylene oxide to branched polyaminecan range Within wide limits, for example, from a 1:1 mole ratio to aratio of l000:l, or higher, but preferably 1 to 200. For example, indemulsification extremely high alkylene oxide ratios are oftenadvantageously employed such as 200-300 or more moles of alkylene oxideper mole of branched polyamine. On the other hand, for certainapplications such as corrosion prevention and use as fuel oil additives,lower ratios of alkylene oxides are advantageously employed, i.e.,1/1025 moles of alkylene oxide per mole of branched polyamine. By propercontrol, desired hydrophilic or hydrophobic properties are imparted tothe composition. As is well known, oxyalkylation reactions are conductedunder a wide variety of conditions, at low or high pressures, at low orhigh temperatures, in the presence or absence of catalyst, solvent, etc.For instance oxyalkylation reactions can be carried out at temperaturesof from 80*200 C., and pressures of from 10 to 200 p.s.i., and times offrom 15 min. to several days. Preferably oxyalkylation reactions arecarried out at 80 to 120 C. and 10 to p.s.i. For conditions ofoxyalkylation reactions see US. Patent 2,792,369 and other patentsmentioned therein.

Oxyalkylation is too well known to require a full discussion. Forpurpose of brevity reference is made to Parts 1 and 2 of US. Patent No.2,792,371, dated May 14, 1957, to Dickson in which particular attentionis directed to the various patents which describe typical oxyalkylationprocedure. Furthermore, manufacturers of alkylene oxides furnishextensive information as to the use of oxides. For example, see thetechnical bulletin entitled, Ethylene Oxide, which has been distributedby the Jefferson Chemical Company, Houston, Texas. Note also theextensive bibliography in this bulletin and the large number of patentswhich deal with oxyalkylation processes.

Acid Mols of Acid Water Exam- Branched Per Mols of Removed e PolyamineBranched Name Grams Polyamme Moles Grams 18A1 N-800 Oleic (282 564 2:12.2 39. 6 18-142... N-800 do 282 1:1 1.9 34.2 19-111.-. N-800 Dimeric(600)- 1,800 3:1 2.9 52. 3 19A N-800 "do 1,200 2:1 2.1 37.8 20A1 N-800Alkenyl Succinic An- 532 2:1

hydride (266). 20-Az N800 do 266 L; L 21A N-800 Diglycolic (134) 134 1:11.0 18 22A N-800 Maleic Anhydride (98).. 98 1:1 23- N-800 Naphthenie(33) Sunap- 330 1:1 2.1 37.8

ti A id 11 The symbol employed to designate oxyalkylation is O.Specifically 1-0 represents oxyalkylated Polyamine N-400.

In the following oxyalkylations the reaction vessel em- 12 tion ishighly exothermic. The reaction mass now contains 1 mol of N-400 and atotal of 22 mols of reacted ethylene oxide.

Example 1-O ployed is a stainless steel autoclave equipped with the 5 Aportion of the Ramon mass of Example is usual devlces for heatmg andheat, control a st1rr.er transferred to another autoclave and anadditional amount and outlet means and the like WhlCh are conventionalin of Eto was added The reaction mass now contains the this type ofapparatus. The stirrer is operated at a speed ratio of 1 mol of N 4O0 to40 mols of Eta of 250 r.p.m. The branched polyamine, Polyamine N- Exam 1400, dissolved in an equal Weight of xylene is charged into P a thereactor. The autoclave is sealed, swept with nitro- The adclltlon ofOXlde t0 Example 143415 gen, stirring started immediately and heatapplied. The finned a molar rat) of 1 mol of N 4O0 to 75 molstemperature is allowed to rise to approximately 100 C. of Bio reachedatwhich time the addition of the alkylene oxide is started Example 6 andadded continuously at such speed as it is absorbed 15 The addition f h lide to Example 1-O is by the reaction mixture. When the rate ofoxyalkylation continued until a molar m, f 1 mo] f 4()0 to 33 slows downappreciably, which generally occurs after mols f 0 is reached about 15moles of ethylene oxide are added or after about E l 1 O 10 moles ofpropylene oxide are added, the reaction vessel xamp e 7 is opened and anoxyalkylation catalyst is added (in 2 The addition of ethylene oxide tothe Example 1-0 is weight percent of the total reactants present). Thecatcontinued until a molar ratio of 1 mol of N-400 to 105 alyst employedin the examples is sodium methylate. mols of EtO is reached. Thereu onthe autoclave is flushed out as before and oxyalky lation completed. Inthe case of oxybutylation, Example 2O1 oxyoctylation, oxystyrenation,and other oxyalkylations, grams of N-400 'gfld H 10 a Conventional etc.,the catalyst is added at the beginning of the operation, stainless steelautoclave. The temperature is ra1sed to 120 C., the autoclave is flushedwith nitrogen and sealed. Example Then 290 grams of propylene oxide(S-mols) are added Using the oxyalkylation apparatus and procedurestated slowly at 120 C. A sample is taken at this point and above, thefollowing compounds are prepared: 400 grams labeled 2O This samplecontains 5 mols of PrO for (1 mol) of Polyamine 400 are charged into astainless each mol of N-400. It is a dark very viscous liquid at steelautoclave, swept with nitrogen, stirring started, and room temperature.autoclave sealed. The temperature is allowed to rise to Example 2-0 aroximately 100 C. and ethylene oxide is injected c r itinuously until220 grams (5 mols) total had been The addfuon of propylene. Oxide to L0115 continued added over a one-half hour period. This reaction is exoas.follows' The autoclave is opened and 35 gFamS 9 thermic and requirescooling to avoid a rise in temperamm: methyltte are added The autoclave1s l ture. The reaction mass is transferred to a suitable congf g fi gPropylene oxlde 1s tainer. Upon cooling to room temperature, thereaction a e deal-e u y unn akdltlonal 2 grams have beenmassisadarkextremelyviscousliquid. 40 reacte sample is ta en at th1spoint and labeled 2O ThlS compound now contains 10 mols of propyleneExample z oxide for each mol of N-400.

The same procedure as Example l-O is used exactly Example 20;, exceptthat 396 grams of ethylene oxide (9 mols) is added to men .052?astraitagitati :1225:?x2221:- iafiieon material is a dark vlscous liquld atroom temperais taken at this point and labeled 3 3 Com Example tains 21mols of propylene oxide for each mol of N-400. The Sam rocedure a E 16 1O s u ed nd 396 At lrkcliom tempfrfiture the product is a dark thickliquid.

e s xam 1 s a grams of eth3llene oxide (9 mols) are added to 400 grams5O 2-O 2 3: 2 6: 2 0 confirmed to Produce examples (1 mol) of PolyamineN-400. After this reaction is A summary of oxyalkylated productsproduced from completed, the autoclave is opened and 20 grams of sodi-N-400 is presented in the following Table II. um methylate are added.The autoclave is then flushed The Roman numerals, (I), (II), and (III)besides the again with nitrogen and an additional 572 grams (13 moles ofoxide added indicate the order of oxide addition mols) of ethylene oxide1s added at C. This reac- (I) first, (II) second and (III) third, etc.

TABLE II.OXYALKYLATED PRODUCTS [Moles of oxide/mole N-400] Ex. 13528I151335 51125 Physical properties Dark viscous liquid.

Semi-solid.

Solid.

TABLE II.Continued Ex. EtO Wgt. PrO Wgt. BuO Wgt Physical propertiesMoles (g.) Moles (g.) Moles (g) 220 40 (II) 2, 320 Dark viscous liquid.484 63 (II) 3, 654 Do. 748 88 (11) 3,872 Do. 2, 332 19 (II) 1, 102Semi-solid. 4, 312 95 (II) 4, 510 Dark thick liquid.

352 19 (I) 1,102 Do. 968 39 (I) 2, 262 Do. 792 96 (I) 5, 568 Do. 4, 080105 (I) 6, 090 D0. ,420 (I) 290 id.

220 18 (II) 1, 044 Dark viscous liquid. 220 5 (III) 290 Do. 396 23 (III)1, 334 Do. 836 19 (II) 1,102 Do. 1, 980 75 (I) 4, 350 Do. 7-01- Octyleneoxide 5 moles, 635 g. Do. 70; Octylene oxide 8 moles, 1,016 g. D0. 801Styrene oxide 4 moles, 480 g. Do. 8O Styrene oxide 7 moles, 840 g. Do.9O1. Epoxide 201 1 mole, 280 g. Solid.

The following table presents specific illustration of compounds otherthan N-400 and its derivatives.

TABLE II-A.OXYALKYLATED PRODUCTS Mols of Oxide Per M01 Ex- Branched oiBranched Polyamine Physical ample Polyamine Properties EtO PrO B1101001.-- 1 Dark viscous Octylene Oxide, Styrene Oxide, 10 mols Epoxide201, 2 mols 5 (III) 4 r Styrene Oxide, 5 mols Octylene Oxide, 10 molsACYLATION THEN OXYALKLATION Prior acylated branched polyamines can beoxyalkylated in the above manner by starting with the acylated branchedpolyamine instead of the unreacted amine. Non-limiting examples arepresented in the following tables. The symbol employed to designate anacylated, oxyalkylated branched polyamine is A0. Specifically 1-A Orepresents acylated, then oxyalkylated polyamine N-400.

Example 3-A O For this'example an autoclave equipped to handle alkyleneoxides is necessary. 1156 grams (1 mole) of 3A (N-400-l-3 moles OleicAcid minus three moles H 0) are charged into the autoclave. Following anitrogen purge and the addition of 120 grams of sodium methylate, thetemperature is raised to135 C. and 5683 grams of EtO (98 mols) areadded. At the completion of this reaction, 2024 grams of PrO (46 moles)are added and the reaction allowed to go to completion. The

resulting polymer is a dark viscous fluid soluble in an aromaticsolvent.

Example 5A O For this example a conventional autoclave equipped tohandle alkylene oxides is necessary. 946 grams of 5A (N-400+3 moleslauric acid minus 3 moles H O) are charged into the autoclave. Thecharge is catalyzed with 100 grams of sodium methylate, purged withnitrogen and heated to 150 C. 480 grams (4 moles) of styrene oxide areadded and reacted for 24 hours with agitation. The resulting product isa dark extremely viscous fluid.

Example 7-A O For this example a conventional autoclave equipped tohandle alkylene oxides is necessary. 1314 grams of 7-A (N-400+4 molespalmitic acid minus 6.2 moles H O) are charged into the autoclave.Following the addition of grams ocE sodium methylate and a nitrogenpurge, the mass is heated to C. 660 grams of EtO (15 moles) are addedand the reaction proceeded to completion. Then 1440 grams of BuO (20mols) are added and again the reaction proceeded to completion. Theresulting polymer is a dark viscous fluid soluble in an aromaticsolvent.

These reactions are summarized in the following table:

[Moles of oxide/mole oi reactant] EtO PrO BuO Ex. Physical PropertiesMoles Wgt. Moles Wgt Moles Wgt.

(e) (a) (a) 1A O1 42 (II) 1, 048 78 (I) 4, 524 Dark, viscous liquid.1-A40- 8 (II) 352 59 (I) 3, 422 Do. 1-A40a 8 (III) 352 18 (II) 1,044 15(I) 1,080 Do. 1-A404 23 (III) 1,018 47 (I) 2,726 10 (II) 720 Do. 3AaO1..12 (I) 528 22 (II) 1, 276 Solid. 34401.... 12 (II) 528 29 (I) 1,682Dark, thick liquid. 3-As0a...- 46 (II) 98 (I) Do. 4-AiOi- 4 Solid. 4A10zD0. 4Ai0s.. Do. Ai.--- Do. 5-AiOz... D0. 5A1Oa Styrene oxide 4 moles,480 grams Dark, viscous liquid. 5Ai04 Octylene oxide 5 moles, 635 grams0. 7-A|0i 15 (I) 660 (II) 1, 440 Dark, thick liquid. 7A1Oz. 10 (II) 440(I) Do. 7A1O 109 (II) 4, 796 210 (I) Do.

23 (I) 1,018 18 (II; Do.

23 (I) 1,018 26 (II D0.

36 (II) 1, 584 78 (I) Do.

32 (I) 1, 408 23 (II) Solid. ilk-A103. 13 (I) 572 49 (II) Do.

The following table presents specific illustration of compounds otherthan N-400 and its derivatives.

TABLE IIIA.ACYLATED, OXYALKYLATED BRANCHED POLYAMINES Mois of Oxide PerM01 0! Reactant Example Physical Properties EtO PrO BuO 18-A201 5 Dark.viscous liquid. 18-Aa0i 10 (II) 60 (I) Do. 18-A10 2 Do. Iii-A104 6 (III)(H 10 (I) Do.

Styrene oxi e, 4 mols 15 (II) Do. (II) 2 (I) Do.

Octylene oxide, 5 mols 80 (II) 10 (111) Do. 2 (II) Do. 4 Do. 8 (I) 1(III) Do. Do. 3 Do. Do. 5 (III) 26 (I) Do. Do. Do. 3 Do. 31-11104.Epoxide 201, 1 moi Do. 33-11101 Styrene oxide, 10 mols Do.

OXYALKYLATION THEN ACYLATION The prior oxyalkylated branched p'olyaminescan be acylated with any of the acylation agents herein disclosed (incontrast to acylation prior to oxyalkylation). Since these reactantsalso have hydroxy group acylation, in addition to reaction with theamino groups noted above, also includes esterification.

The method of acylation in this instance is similar to that carried outwith the polyamine itself, i.e., dehydration wherein the removal ofwater is a test of the completion of the reaction.

Example 1-O A One mole of 1-0 (620 grams) is mixed with three moles ofacetic acid- (180 grams) and 400 ml. of xylene at room temperature. Thetemperature is raised slowly to 120-130 C. and refluxed gently for onehour. The temperature is then raised to 150-160" C. and heated until 3moles of water and all of the xylene are stripped oif. The dark productis water-soluble.

Example 2-O A One mole of 2-0.; (2894 grams) is mixed with one mole ofpalmitic acid (256 grams) at room temperature. Vacuum is applied and thetemperature is raised slowly until one mole of water (18 grams) isremoved. This product is a dark viscous liquid.

Example 6-O A One mole of 6-0 (7450 grams) is mixed with 500 grams ofxylene and heated to C. One mole of diglycolic acid (134 grams) is addedslowly to prevent excessive foaming. The temperature is raised to -150"C. and held until one mole of water has evolved. This product is thediglycoiic acid fractional ester of 6-0 A white precipitate forms duringthis reaction which can be removed by filtration. Analysis shows theprecipitate to be sodium acid diglycollate, a reaction product of thecatalyst and digiycolic acid. The filtered product is a dark viscousliquid at room temperature.

Table IV contains examples which further illustrate the invention. Thesymbol employed to designate oxyalkyiated, acylated products is 0A.

TABLE IV.OXYALKYLATED. THEN ACYLATED BRANCHED POLYAMINE N-400 Acyiatingagent Water removed Physical Ex. properties Moles oi Wgt., Wgt. Nameacyiating grams Moles (g) agent 3 180 3 54 ark liquid. 1 282 1 18 Do. 2568 2 .36 Solid. 1 200 1 18 Dark liquid. 2-OzA-.. .Myristic 2 457 2 36Do. 2-O4A -Pa.lmitic 1 256. 4 1 18 Do. 4-01A.-- Oleic 2 564 2 36 Solid.4-03A.- Ricinoieic... 1 298. 5 1 18 Diilllifld q 501A.. Abietic acid. 1302.4 1 18 Dark solid 5-0 Tall oil--- 1 1 18 Dark liquid. 1 280.4 1 18Do. 2 564 2 36 D0. 1 98 1 i8 Viscous hydride. liquid. 6-0511".Diglycollc--- 1 134 1 18 Do. 7-011... Lauric 2 400 2 36 ark liquid.8-O1A-. Stearic 1 284 1 18 id.

The following table presents specific illustration of compounds otherthan N-40O and its derivatives.

TABLE IVA.OXYALKYLATED, THEN .ACYLATED BRANCHED POLYAMINE Water Re- Molsof moved Physical Example Name Acylating Wt. in Proper- Agent Grams tiesMols Wt. in

Grams III-03A--- Stearic 1 284 1 18 Solid. 11-0 11-.. Laurie 2 400 2 36Viscous liquid. 11-0011--. Diglycolic.-- 1 134 1 18 Dark liquid. 12-O1AMaleio an- 1 98 Viscous hydride liquid 1301A Oleic 2 564 1 18 Do. 14-02Linoleic 1 280.4 1 18 Do. 15-0111.-- Tall oil 1 175 1 18 Do. 16-03Abieticacid- 1 302 1 18 Solid. 17OA Ricinoleic..- 1 298 1 18 Viscousliquid 18OA- Oleic 2 564 2 36 Do. 20-01 Palmitic. 1 256 1 18 Solid. 20-011--- Myristic 2 457 2 36 D0. 21-01 Laurie 1 200 1 18 D0. 21-00 Stearic2 568 2 36 Do. 22-0211--. Oleio 1 282 1 18 Viscous liquid. 23-OzA---Acetic 1 60 1 18 Do. 24'O2A--- Diphenolic 1 286 1 18 Do. 25-0111.-.Tereph- 1 166 1 18 Solid.

thalic. 25-0411--. Naphthem'c. 2 330 2 36 Viscous liquid. 25-0511- 1330 1. 9 34 D0. 26-0111--- 1 122 1 18 Do. 26-OzA--. 1 200 1.8 32 Do.

HEAT TREATMENT OF OXYALKYLATED PRODUCTS The oxyalkylated productsdescribed herein, for example, those shown in Table II relating tooxyalkylated branched polyamines and those in Table 111 relating tooxyalkylated, prior acylated, branched polyamines can be heat treated toform useful compositions.

In general, the heat treatment is carried out at 200- 250 C. Underdehydrating conditions, where reduced pressure and a fast flow ofnitrogen is used, lower temperatures can be employed, for example 150200C.

Water is removed during the reaction, such as by means of a side trap.Nitrogen passing through the reaction mixture and/or reduced pressurecan be used to facilitate water removal.

The exact compositions cannot be depicted by the usual chemical formulasfor the reason that the structures are subject to a wide variation.

The heat treatment is believed to result in the polymerization of thesecompounds and is effected by heating same at elevated temperatures,generally in the neighborhood of ZOO-270 C., preferably in the presenceof catalysts, such as sodium hydroxide, potassium hydroxide, sodiumethylate, sodium glycerate, or catalysts of the kind commonly employedin the manufacture of superglycerinated fats, calcium chloride, iron andthe like. The proportion of catalyst employed may vary from slightlyless than 0.1%, in some instances, to over 1% in other instances.

Conditions must be such as to permit the removal of water formed duringthe process. At times the process can be conducted most readily bypermitting part of the volatile constituents to distill, andsubsequently subjecting the vapors to condensation. The condensedvolatile distillate usually contains water formed by reaction. The watercan be separated from such condensed distillate by any suitable means,for instance, distilling with xylene, so as to carry over the water, andsubsequently removing the xylene. The dried condensate is then returnedto the reaction chamber for further use. In some instances, condensationcan best be conducted in the presence of a high-boiling solvent, whichis permitted to distill in such a manner as to remove the water ofreaction. In any event, the speed of reaction and the character of thepolymerized product depend not only upon the orginal reactantsthemselves, but also on the nature and amount of catalyst employed, onthe temperature employed, the time of reaction, and the speed of waterremoval, i.e., the effectiveness with which the water of reaction isremoved from the combining mass. Polymerization can be effected withoutthe use of catalysts in some instances, but such procedure is generallyundesirable, due to the fact that the reaction takes a prolonged periodof time, and usually a significantly higher temperature. The use ofcatalyst such as iron, etc. fosters the reaction.

The following examples are presented to illustrate heat treatment. Thesymbol used to designate a heat treated oxyalkylated polyamine is OH andan acy-lated, oxyalkylated product is AOH. In all examples 500 grams ofstarting material and a temperature of 225-250 C. are employed.

Example 1-O H A conventional glass resin vessel equipped with a stirrerand water trap is used. Five hundred grams of lO are charged into theabove resin vessel along with five grams of CaCI The temperature israised to 225-250 C. and heated until 50 grams of water (2.8 mols) areevolved. This process takes 7.5 hours of heating. The product is anextremely viscous material at room temperature. However, upon warmingslightly this product dissolves easily in water.

Example 2O H The process of the immediately previous example is repeatcdusing 2-0 but substituting sodium methylate for calcium chloride. Theproduct is a dark, viscous, water-soluble material.

Example 6O H The process of Example 1-O H is repeated using 6-0 butsubstituting powdered iron for calcium chloride.

TABLE V.HEAT TREATED (l) OXYALKYLATED AND (2) AOYLATED, OXYALKYLATEDPOLYAMINE N-400 Water Removed Ex. Catalyst, Time in 5 grams Hours Wgt.Moles 63 3. 5 8.0 56 3. 1 Q. 3 40 2. 2 10.0 31 1. 7 7. 5 61 3. 4 8. 033 1. 8 6.8 63 3. 5 8.0 3A.301H. Sodium 47 2.6 8. 5

Methylate 7A1O2H NaOH 27 1. 5 7. 5 9-A303H OaOH 50 2. 8 8. 0 11A101H.KOH 54 3.0 8. 5

All of the above products are dark, viscous liquids.

The following table presents specific illustration of compounds otherthan N-400 and its derivatives.

TABLE VA.HEAT TREATED (1) OXYALKYLATED AND (2) AOYLATED. OXYALKYLAIEDBRANCHED POLYAMINE Example Catalyst Wt. of Water Mols of 1120 Time in (5grams) Removed Removed Hours 50 2.8 8. 0 54 3.0 8. 5 40 2. 2 10.0 56 3.1 9. 3 63 3. 6 8. 0 58 3. 2 7. 6 29 1. 6 8. 5 18-A2OaH-.. 50 2. 8 7. 525AiOzH- 29 1. 6 8. 5 26A102H 63 3. 5 8. 0 27.A1OaH 33 1. 8 6. 831-A101H--- 27 1. 5 7. 5 33-A1O1H--- 50 2. 8 8.0

All of the above products are dark, viscous liquids.

ALKYLATION Alkylation relates to the reaction of the branched polyamineand derivatives thereof with alkylating agents.

Any hydrocarbon halide, e.g. alkyl, alkenyl, cycloalkenyl, aralkyl,etc., halide which contains at least one carbon atom and up to aboutthirty carbon atoms or more per molecule can be employed to alkylate theproducts of this invention. It is especially preferred to use alkylhalides having between about one to about eighteen carbon atoms permolecule. The halogen portion of the alkyl halide reactant molecule canbe any halogen atom, i.e., chlorine, bromine, fluorine, and iodine. Inpractice, the alkyl bromides and chlorides are used, due to theirgreater commercial availability. Non-limiting examples of the alkylhalide reactant are methyl chloride; ethyl chloride; propyl chloride;n-butyl chloride; sec-butyl iodide; t-butyl fluoride; n-amyl bromide;isoamyl chloride; n-hexyl bromide; n-hexyl iodide; heptyl fluoride;2-ethylhexyl chloride; n-octyl bromide; decyl iodide; dodecyl bromide;7-ethyl-2-methyl-undecyl iodide; tetradecyl bromide; hexadecyl bromide;hexadecyl fluoride; heptadecyl chloride; octadecyl bromide; docosylchloride; tetracosyl iodide; hexacosyl bromide; octacosyl chloride; andtriacontyl chloride. In addition, alkenyl halides can also be employed,for example, the alkenyl halides corresponding to the above examples. Inaddition, the halide may contain other elements besides carbon andhydrogen as, for example, where dichloroethylether is employed.

The alkyl halides can be chemically pure compounds or of commercialpurity. Mixtures of alkyl halides, having carbon chain lengths fallingwithin the range specified hereinbefore, can also be used. Examples ofsuch mixtures are mono-chlorinated wax and mono-chlorinated kerosene.Complete instructions for the preparation of mono-chlorowax have beenset forth in United States Patent 2,238,790.

Since the reaction between the alkyl halide reactant and the branchedpolyamine is a condensation reaction, or an alkylation reaction,characterized by the elimination of hydrogen halide, the generalconditions for such reactions are applicable herein. It is preferable tocarry out the reaction at temperatures of between about 100 and about250 0., preferably between about 140 C. and about 200 C., in thepresence of a basic material which is capable of reacting with thehydrogen halide to remove it. Such basic materials are, for example,sodium bicarbonate, sodium carbonate, pyridine, tertiary alkyl amines,alkali or alkaline earth metal hydroxides, and the like.

It is preferred to perform the reaction between the alkyl halidereactant and the branched polyamine reactant in a hydrocarbon solventunder reflux conditions.

The aromatic hydrocarbon solvents of the benzene series 20 areespecially preferable. Non-limiting examples of the preferred solventare benzene, toluene, and xylene. The amount of solvent used is avariable and non-critical factor. It is dependent on the size of thereaction vessel and on the reaction temperature selected. For example,it will be apparent that the amount of solvent used can be so great thatthe reaction temperature is lowered thereby.

The time of reaction between the alkyl halide reactant and the branchedpolyamine is dependent on the weight of the charge, the reactiontemperature selected, and the means employed for removing the hydrogenhalide from the reaction mixture. In practice, the reaction is continueduntil no more hydrogen halide is formed. In general, the time ofreaction will vary widely such as between about four and about tenhours.

It can be postulated that the reaction between the alkyl halide reactantand the branched polyamine results in the formation of products wherethe alkyl group of the alkyl halide has replaced a hydrogen atomattached to a nitrogen atom. It is also conceivable that alkylation ofan alkylene group of the branched polyamine can occur. However, theexact composition of any given reaction product cannot be predicted. Forexample, when two moles of butyl bromide are reacted with one mole ofPolyamine N-400, a mixture of mono-, diand triand higher N-alkylatedproducts can be produced. Likewise, the alkyl groups can be substitutedon diflerent nitrogen atoms in different molecules of the branchedpolyamine.

Thus, the term Alkylation as employed herein and in the claims includesalkenylation, cycloalkenylation, aralkylation, etc., and otherhydrocarbonylation as well as alkylation itself.

In general, the following examples are prepared by reacting the alkylhalide with the branched polyamine at the desired ratio in the presenceof one equivalent of base for each equivalent HCl given off during thereaction. Water formed during the reaction is removed by distillation.Where the presence of the anions, such as chlorine, bromine, etc., isnot material and salts and quaternary compounds are desired, no base isadded.

The following examples are presented to illustrate the alkylation of thebranched polyamines.

Example 5-K One mole of each of the following: tetradecylchloride,Polyamine N-400, and sodium bicarbonate are placed in a reaction vesselequipped with a mechanical stirrer, a thermometer and a condenser refluxtake-off for removal of water from the reaction as it is evolved in anazeotropic mixture of water and a hydrocarbon solvent. The refluxtake-off is filled with xylene. The stirred reactants are heated toabout C. whereupon an exothermic reaction causes the temperature to riseto about C. The reaction temperature is then increased to C. and heldthere for two hours. Then, xylene is added to the reaction vessel in anamount sufiicient to cause a xylene reflux to take place at atemperature of ISO- C. The reaction is continued for six hours or untilthe theoretical amount of water is removed. Thereupon, an equal volumeof xylene is added to the reaction mixture and the resultant solution isfiltered. This filtrate is then evaporated under reduced pressure toyield a dark amber oil. No halogen was present in this product asevidenced by a negative Beilstein copper wire test.

Example 5K X The above reaction is repeated except that no sodiumbicarbonate is employed in the reaction. The reaction product containedchlorine.

The reactions shown in the following table are carried out in a similarmanner. Each reaction in the table is carried out in two ways( 1) in thepresence of base as in 5K to yield the halogen-free alkylation productTable VI and (2) in the absence of base to yield halogen con; tainingproducts in the manner of 5K X Table VII.

The alkylated products of this invention contain pri- TABLE VI.Contiuuedmary, secondary, tertiary, and quaternary amino groups. By controllingthe amount of alkylation agent employed Ratio, Moles of Alkyl- Physicaland the conditions of reaction, etc., one can control the g g e ig i l yfl li z f ti s type and amount of alkylation. For example, by reactionDerivatives less than the stoichiometric amount of alkylation agent onecould preserve the presence of nitrogen-bonded hydro- 3-111---Z-ethyl-hexyl chlo- 3:1 Visco s gen present on the molecule and byexhaustive alkylation ride 5:1 in the presence of sufficient basicmaterial, one can form 711 Do. more highly alkylated compounds. 5 Themoles of alkylating agent reacted with the branched 3:1 dDo. polyaminewill depend on the number of alkylation reac- 'r r 'gf 2313 tivepositions contained therein as well as the number of K d Sqlid moles ofalkylating agent one Wishes to incorporate into 21 8 the molecule.Theoretically every hydrogen bonded to a HQ 0ctadecy1ch10ride 1:1initrogen atom can be alkylated. We have advantageously "do 3:1 freacted 110 moles of alkylating agent per moles of Polydo 4:1 i Do.amine N-400, but preferably 1-6 moles. With Polyamine Bemyl cmmde 1:1 3213 N-800 and N-1200, twice and three times as many moles 7- g0 5:1 ofalkylating agent can be employed respectively, i.e., with mam-55 5:Polyamine N800, 1-20 moles, preferably 1-12,; with a ig PolyamineN-12o0, 1-30 but preferably 1-18. Optimum 3 3 3; alkylation will dependon the particular application. Dodecenyl chloride/0 S In addition, thealkyl halide may contain functional 3:1 5% groups. For example,chloroacetic acid can be reacted s with the branched polyamines to yielda compound cong icy enzy c o- 2.1 0 taming carboxylic acid groups 10 K-----g 33- a-" 0 Z PN CH2COOH 1,4-dich1orobutene-2.. 1:2 vi s nzlo u ewherein P llS the residue of the poly-amine. 133; In addition, thebranched polyamine can be alkylated 1:2 Do. with an alkyl halide such asalkyl chloride and then re- 3:1 Do acted with chloroacetic acid to yieldan alkylated poly- 6:1 13o. amine containing carboxylic acid groups 3:

5:1 SemIiI-d 9' C iaHn5N) n P (C H10 0 H) n Benzylchloride 8:1 Solid hlThe symbol employed to designate an al kylated polyfiiii g flilfig 3;} 333 amine is K. Where the product is a salt or a quaternary Ethylenedichloride 33 product the symbol is KX. s-olAK 1,4-dichlorobuteue-2 4:1in).

TABLE VI ALKYLATED PRODUCTS 1-A40zK Dodecy1ch1oride 3:1 Sem i-d SO 1 A OK -A 1b id 4:1 Vis 5 Ratio, Moles ofAlkyl- Physical 7 n my mm e in fiiidEx. A ylating at Agent/Mole of p 4-0111]: 1,4-xy1ylene diehlo- 3:1 Do.

Agent Polyamine ifle or ties ride.

Derivatives 6-02HK Methyl chloride 6:1 Liquid. 7-A1O2HK----Dichlorodiethylethen 4:1 vilsicoiifi1 11 1-K1 Butyl chloride 1:1Vilscflll g 11-A O HK do 4:1 in).

lqlll 1-K; d0 3:1 Do. 1-Ka-.. --d0 5:1 D0. gjg: fif g 3: The followingtable presents specific illustration of compounds other than N -400 andits derivatives.

TABLE VI-A.ALKYLATED PRODUCTS Ratio, Mols of Branched Alkylating AgentPer Physical Example Polyamine Alkylatmg Agent Mol of Branched Prop-Polyaniine or erties Derivatives Benzyl chloride 2:1 Viscous liquid mgoBo. 0 1 0.

Dichlorodiethylether 1:1 Semid 3 1 i 0 I 0. Allyl chloride 1:1 Viscousliquid g0 1130. O Z 0. Butyl ch1oride 1:1 D0. (1 3:1 D0. 5:1 D0. e 2 O.Dodecenyl chlorid 1:1 Do. Dimethyl sulfate 2:1 D0. glilchllogidiehyletBo. y e on e o. Oetadecyl chlori 3:1 D0. nAmyl bromide 1:1 Do.1lgenfilyl chlortide. g0. 10 oropen 8,119,- Z 0- 25A1OHK N-1200 Methylchloride 1:1 Do.

TABLE AND QUATERNARY PRODUCTS OF The following table presents specificillustration of ALKYLATED N400 AND DERIVATIVES compounds other thanN-400 and its derivatives.

Ratio, Moles of Physical Ex. Alkylating Agent Alkylating Agent] of Prop-Polyamine N-400 erties or derivative TABLE VIIA.-SALT AND QUATERNARYPRODUCTS 0F Butyhhlmde E323 ALKYLATED BRANCHED POLYAMINE AND DERIVA- mmr3:1 Do. TWES All b 1 1 3 2-KX 1 romi e o. z-wm f. m? 4=1 Do. 10 Ratio ofAlkylating Physical 2-167 do 6:1 Do. Example Alkylating Agent Agent/0ilfoiyamme Proper- 3-K:X 2-eiil11yl-hexylch1c 3:1 Do. or Derivative tiesI 8. 3- X --do 5:1

K2 do 7:1 Ethylene dichloride. 2:1 Solid.

Dodeeyl chloride 2:1 n-Amyl bromide..- 3:1 Do. Dichlorodiethyl- 4:1 Do..do 3:1 ether. dn 5:1 Dimethyl sulfate.-- 3:1 Do. Tetradecyl chloride-1:1 Methyl ch1or1de 2:1 Do. 1,4-xylene dlehlo- 5:1 D0. dn 3:1 ride. do6:1 D0decy lbenzy1 8:1 Semi;

Octadecyl chloride" 1:1 chloride. solid.

rin 3:1 1,4-dichlorobutene-2- 3:1 Do. .do 4:1 Benzyl chloride.-." 4:1Do. Benzyl chloride 1:1 Methyl chloride..- 3:1 Do. Ethylene dichloride-2: 1 Do. do 5:1 Dodecyl chloride 1:1 Do. -do 3: 1 Dichlorodiethyl- 1 :1Solid.

Allyl chloride 3:1 ether.

Benzy1chloride 3:1 Do. 4:1 do 2:1 Do. do 6:1 1:1 D0. Dodecenyl ch1oride1:1 5:1 Do. solid, 33-Ai0vKY 4:1 Do. do 3:1 id. 110:AKX-- 3:1 Do. do 5:1Do. 18-OAKX..- 3:1 D0.

Dodecyibenzyl 2: 1 D0.

chloride. 14O:HKX..-- 2:1 Do. do 4:1 Do. 25-A1O2HKX. 1:1 Do. do 5:1 Do.i,4-dichlorobutene-2- 1 2 Viscous liquid. (in 2:1 Do. in 3:1 D0.1,4-xylylene dichlo- 1:2 Do.

ride.

:10 3:1 D0. ALKYLATED THEN ACYLATION Dichlorodiethyl- 1: 1 D 0.

3:1 Sem1 The alkylated material prepared above can be further d m s olid. treated with acylating agent where residual acylatable amino groupsare still present on the molecule. The acylag fiy gy dg 25% L1 33- tionprocedure is essentially that described above whereinDimeih1s3iia6.'.-.. 4Z1 vil cous galrlbgxylic acidsdreact with thealkyilated (polyamine under iquide y rating con itions to form ami es aneye ic amidines. Elgliiilgfilffigglflg; ii 53; The product depends onthe ratio of moles of water re- 4 Dodecylchloride-u- 311 f moved foreach carboxylic acid group, 1.e., 1 mole water/ 7-A1OlKX- n-Amylbromide4:1 vilseouig 1 Incl/e1carbfxylicbessentiallv gmides; more than 1 moleiqu water mo e car oxy ic aci group, essentially cyclic 'fififi dmmo'amidines, such as imidazolines. 60:HKX Methy chl0r d 611 Such compoundsare illustrated in the following table.

z 7 4 1 23 The symbol employed to designated alkylated acylated11-ArO1HKX- ..---do products is KA and acylated, alkylated, acylatedproducts is AKA.

TABLE VIIL-ACYLATED, PRIOR ALKYLATED BRANCHED POLYAMINES Moles ofAcylat- Moles Ex. Aeylating Agent ing Agent/Mole Wgt. Water Physical ofN 400 01: Removed Properties Derivative 14? A O 2 564 3. 1 Viscousliquid. Z-KzA Steane 3 852 3. 0 Solid. 3-KzA Laurie 2 400 2. 8 Viscousliquid. 4-K1A Palmitic- 3 769 4. 1 Do. 5-KzA Dimeric 1 600 2. 2 Do. KAikenyl (0m) 1 266 0. 5 Solid.

sueeinlc anhydnd 1 282 1. 7 Viscous liquid. 2 564 3.1 Do. 2 400 2. 8 D0.2 598 3. 0 D0. 1 282 l. 5 D0. Alkenyl 1 266 Solid.

suecinie anhydride. 3A:KA:-.-- Oleie 1 282 1. 5 Viscous liquid.

The following table presents specific illustration of compounds otherthan N-400 and its derivatives.

free, to eliminate undesirable side reactions. At room temperature,slowly add 53 grams of acrylonitrile (1 mol) TABLE VIII*A.'-ACYLATED,PRIOR ALKYLATED BRANCHED OLEFINATION (Olefination relates to thereaction of the polyamine and derivatives with olefins) The compositionsof this invention, including the branched polyamine itself as well asreaction products thereof containing active hydrogens, can be reactedwith unsaturated compounds, particularly compounds containing activateddouble bonds, so as to add the polyamine across the double bonds asillustrated herein:

Where the compound contains an additional active hydrogen, otherunsaturated molecules can be added to the original molecule for example:

Where one or more active hydrogens are present at another reactive site,the following reaction could take place:

The reaction is carried out in the conventional manner such asillustrated, for example, in Synthetic Organic Chemistry, Wagner andZook (Wiley, 1953), page 673.

Non-limiting examples of unsaturated compounds which can be reacted withthe polyamine and derivatives thereof including thefollowingacry1onitrile, acrylic and methacrylic acids and esters,crotonic acid and esters, cinnamic acid and esters, styrene, styrenederivatives and related compounds, butadiene, vinyl ethers, vinylketones, maleic esters, vinyl sulfones, etc.

In addition, the polyamine and derivative thereof containing activehydrogens can be used to prepare telomers of polymer prepared from vinylmonomers.

The following are examples of olefination. The symbol employed todesignate olefination is U and alkylation, olefination KU.

Example 1-U The olefination reaction is carried out in the usual glassresin apparatus. Since the reaction is that of a double bond with anactive hydrogen, no Water is eliminated. The reaction is relativelysimple, as shown by the following example:

Charge 400 grams of N-400 (1 mol) into glass resin apparatus. Careshould be taken that the N-400 is water- The reaction proceeds smoothlywithout the aid of a catalyst. Warm gently to 100 C. and stir for onehour.

Example 6-U To 800 grams of N-400 (2 mols) in 800 grams of xylene, add124 grams of divinyl sulfone (1 mole) at room temperature. This reactionis exothermic and care must be taken to prevent an excessive rise intemperature which would cause cross-linking and insolubilization.

Example 3-O U Same reactions as Example 1-U except that 1 mol of methylacrylate is substituted for acrylonitrile and 3O is substituted for theN-400. Part of this product is thereupon saponified with sodiumhydroxide to form the fatty amino acid salt.

Further examples of the reaction are summarized in the following table:

TABLE IX.OLEFINAT1ON Moles of Olefin] Compound Olefin Mole of PolyamineTime Tempera- N-400 or Polyamine ture, G.

N-400 Derivative Acrylonitrile 1/1 1 hr- 80-100 Methyl meth- 1/1 1 hr80-100 aerylate. do 3/1 1 hr 80-100 Ethyl cinna- 1/1 2 hrs.-- 120 mate.Ethyl crotonate. 1/1 2 hrs 120 Di-gctyl male- 1/1 2 hrs... 150

a e. Divinyl sulfone. 1/2 30 min- Styrene 1/1 30 min 90 do 3/1 30 min-90 Lauryl meth- 3/1 1 hr 120 acrylate. 9-U Divinyl sulfone- 1/2 30 min-90 4A3-U1 Methyl meth- 1/1 1 hr acrylate. 4A3Uz Divinyl sulfone- 1/2 906K1U Acrylonitrile 2/1 70 4A1O1U Methyl-acrylate 1/1 90 U 1/1 90 l/l 901/1 90 1/1 90 1/1 90 1-O3KU.-- 1/1 90 TABLE IXA.OLEFINATION Schilfs baseis present on the branched amino group rather than on the terminal aminogroup, etc.

Mols of Olefin/M01 Branched oi Branched Poly- Temp., Example PolyamineOlefin amine or Branched Time C.

Polyamine Derivative Acrylonitrile 1:1 1 hr... 80-100 Styrene 1:1 1hr... 80-100 Dlvinyl sulfone 1 :1 1 hr- 80-100 Di-ctylmaleate 1: 1 1 hr-125 Acrylonitrile 2:1 30 m 80-100 Methylacrylate 1:1 30 min 80-100 Ethylcrotonate- 2:1 30 mm- 120 Divinyl sulfone. 2:1 30 min- 120 Ethylclnnamate 1:1 2 hrs 120 Di-oct 1 maleate. 1: 1 2 hrs. 120 Methy meth-1:1 1 hr. 100

acrylate. Styrene 2:1 1 hr 100 Acrylonitrlle 2:1 1 hr- 100 Ethylcinnamate. 1:1 1 hr- 110 Ethyl crotonate-.. 1: 1 2 hrs. 120 Dlvinylsuli'one- 2:1 1 hr- 80 Lanryl meth- 3:1 2 hrs..- 130 acrylate. 25-A102HUAcrylonltrile 1:1 1 hr- 90 16-K3HXU Divinyl sulfone-.. 1:1 1 hr- 90 K1UStyrene 4:1 1 hr 90 33A101KU dn 2:1 1 hr- 90 A1O;HKU .do 1:1 1 hr- 90CARBONYLATION A wide variety of aldehyde may be employed such as(Carbonylation relates to the reaction of the branched polyamine andderivatives with aldehydes and ketones) Where primary amino groups arepresent on the polyamine reactants, Schitfs bases can be formed onreaction with carbonyl compounds. For example, where an aldehyde such assalicylaldehyde is reacted with Polyamine N-400 in a ratio of 3 moles ofaldehyde to 1 mole of Lesser molar ratios of aldehyde to polyamine wouldyield monoor di- Schitfs base rather than a tri Schiffs base such as andother isomeric configurations, such as where the aliphatic, aromatic,cycloaliphatic, heterocyclic, etc., including substituted derivativessuch as those containing aryloxy, halogen, heterocyclic, amino, nitro,cyano, carboxyl, etc. groups thereof. Non-limiting examples are thefollowing:

Aldehydes Benzaldehyde 2-methylbenzaldehyde 3-methylbenzaldehyde4-methylbenzaldehyde Z-methoxybenzaldehyde 4-methoxybenzaldehydea-naphthaldehyde b-naphthaldehyde 4-phenylbenzaldehyde Propionaldehyden-Butyraldehyde Heptaldehyde Aldol 2-hydroxybenzaldehyde2-hydroxy-6-methylbenzaldehyde 2-hydroxy-3 -methoxybenzaldehyde2-4-dihydroxybenza ldehyde 2-6-dihydroxybenzaldehyde2-hydroxynaphthaldehyde-1 l-hydroxynaphthaldehyde-Z Anthrol-Z-aldehyde-lZ-hydroxyfluorene-aldehyde-1 4-hydroxydiphenyl-aldehyde-33-hydroxyphenanthrene-aldehyde-4 1-3-dihydroxy-2-4-dialdehydebenzeneZ-hydroxy-S-chlorobenzaldehyde 2-hydroxy-3 5-dibromobenzaldehyde2-hydroxy-3-nitrobenzaldehyde 2-hydroxy-3-cyanobenzaldehyde2-hydroxy-3-carboxybenzaldehyde 4-hydroXypyridine-aldehyde-34-hydroxyquinoline-aldehyde-3 7-hydroxyquinoline-aldehyde-8 FormaldehydeGlyoxal Glyceraldehyde Schiffs bases are prepared with the polyamines ofthis invention in a conventional manner such as described in SyntheticOrganic Chemistry by Wagner and Zook (1953, Wiley), pages 728-9.

Where more extreme conditions are employed, the products may be morecomplex wherein the carbonyl reactant instead of reactingintramolecularly in the case of Schiffs base may react intermolecularlyso as to act as a bridging means between two or more polyaminocompounds, thus increasing the molecular Weight of the polyamine asschematically shown below in the case where fiormaldehyde is thecarbonyl compound:

In addition to increasing the molecular Weight by means of aldehydes,these compounds result in the formation of cyclic compounds. Probablyboth molecular weight increase and cyclization occur during thereaction.

The following examples illustrate the reaction of carbonyl compoundswith branched polyamines. The symbol employed to designate carbonylationis C, acylation, carbonylation AC, and alkylation, carbonylation SKCJIExample 1-C Charge 400 grams of N400 and 400 grams of xylene into aconventional glass resin apparatus fitted with a stirrer, thermometerand side-arm trap. Raise temperature to 120 C. and slowly add 122 gramsof salicylaldehyde (1 mol). Hold at this temperature for 2 hours. Vacuumis then applied until all xylene is stripped oil. The reaction mass is athick dark liquid which is soluble in water.

Example 6-C Using the same apparatus as above, charge 400 grams ofN-400. While stirring, add slowly at room temperature 82 grams of 37%aqueous formaldehyde (1 mol of HCHO). This reaction is exothermic andthe temperature must be controlled with an ice bath. After theexothermic reaction has ceased, raise temperature to 100 C. The reactionmass may be stopped at this point. It is a viscous water-solublematerial. However, it is possible to continue heating under vacuum untilall of the water has been eliminated. Cross-linking occurs with thisprocedure and care must be taken to prevent insolubilization.

Further examples of this reaction are summarized in the following table:

TABLE X.-CARBONYLATION Compound Aldehyde Mol. Temp., Time Ratio "0.

1/1 120 2 hrs. 2/1 120 2 hrs. .do 3/1 120 2 hrs. Zhydroxy-Il-methoxyl/l130 4 hrs.

benzaldehyde.

2/1 130 4 hrs. 3/1 130 4 hrs. /1 130 4 hrs. 1/1 110 1 hr. 2/1 110 1 hr.3/1 110 1 hr. 3/1 90 2 hrs. 3/1 130 5 hrs. 3/1 2 hrs. Glyoxal 2/1 100 1hr. Glyceraldehyde 2/1 135 3 hrs. Furfuraldehyde 2/1 150 1 hr.Salicylaldehyde 1/1 120 2 hr 1/1 120 2 hrS. 1/1 120 2 hrs. 2/1 120 2hrs.

1 Start 25 0., raise to 100 C.

The following table presents specific illustration of compounds otherthan N-400 and its derivatives.

TABLE XA.CARBONYLATION Compound Branched Aldehyde M01. Temp., TimePolyamine Ratio C.

10-Ct N800 Formaldehyde 2:1 1 hour. 10-01 N-800 do 1:1 80 Do. 10-0:N-800 do 0. 5:1 80 Do. 11-01 N1200 Aeetaldehyde.-- 2:1 Do. 11-Cz N1200d0 1:1 100 D0. 0 do 0. 5:1 100 D0. Salicylaldehyde. 3: 1 Do. do 2:1 120Do. do 1:1 120 D0. Benzaldehyde--. 3:1 110 Do. do 2:1 110 D0. 1:1 110D0. 1:1 105 Do. 0. 5:1 105 D0. do 0.25:1 105 D0. Glyceraldehyde- 1:1 2hours do 0. 5:1 130 Do Furfuralde- 1:1 80 1 hour hyde. 12-O1HUC do 0.5:1 80 D0.

The examples presented above are non-limiting examples. It should beclearly understood that various other combinations, order of reactions,reaction ratios, multiplicity of additions, etc. can be employed. Whereadditional reactive groups are still present on the molecule, thereaction can be repeated with either the original reactant or anotherreactant.

The type of compound prepared is evident from the letters assigned tothe examples. Thus, taking the branched polyamine as the startingmaterial, the following example designations have the following meaning:

Example designation: Meaning (1) A Acylated. (2) A0 Acylated, thenoxyalkylated. (3) AOA h. Acylated, then oxyalkylated,

then acrylated. (4) AOH Acylated, then oxyalkylated,

then heat treated. (5) AX Salt or quaternary of (l). (6) AOX Salt orquaternary of (2). (7) AOAX Salt or quaternary of (3). (8) AOHX Salt orquaternary of (4). (9) O oxyalkylated. (10) 0A Oxyalkylated, thenacylated. (11) OH oxyalkylated, then heat treated. (12) K Alkylated.(13) KX Salt or quaternary of (12). (14) KA Alkylated, then acylated.(15) AK Acylated, then alkylated. (16) AKX Salt or quaternary of (15).(17) OK Oxyalkylated, then alkylated. (18) OKX Salt or quaternary of(17). (19) C Carbonylated. (20) AC Acylated, then carbonylated. (21) KCAlkylated, then carbonylated. (22) CO Carbonylated, then oxyalkylated.(23) U Olefinated. (24) AU Acylated, then olefinated. (25) KU Alkylated,then olefinated. (26) KUX Salt or quaternary of (25).

USE AS A CHELATING AGENT This phase of the invention relates to the useof the compounds of our invention as chelating agents and to thechelates thus formed.

Chelation is a term applied to designate cyclic structures arising fromthe combination of metallic atoms with organic or inorganic molecules orions. Chelates are very important industrially because one of theunusual features of the chelate ring compounds is their unusualstability in which respect they resemble the aromatic rings of organicchemistry. Because of the great aifinity of chelating compounds formetals and because of the great stability of the chelates they form,they are very important industrially.

The compositions of this invention are excellent chelating agents. Theyare particularly suitable for forming chelates of great stability with awide variety of metals.

Chelating metals comprise magnesium, aluminum, arsenic, antimony,chromium, iron, cobalt, nickel, palladium, and platinum. Particularlypreferred of such metals as chelate constituents are iron, nickel,copper and cobalt.

The chelates formed from the compositions of our invention are useful asbactericidal and fungicidal agents, particularly in th case of thecopper chelates. In addition the chelates can be employed to stabilizehydrocarbon oils against the deleterious effects of oxidation.

In general, these chelates are prepared by adding a sufficient amount ofa metal salt to combine with a compound of this invention. They areprepared by the general method described in detail by Hunter andMarriott in the Journal of the Chemical Society (London), 1937, 2000,which relates to the formation of chelates from metal ions andsalicylidene imines.

The following examples are illustrative of the prepar-ation of thechelates.

Example 8-A To a solution of 0.1 mole of the chelating agent of Example8-A in alcohol is added 0.1 mole of cupric acetate monohydrate. Aftermost of the alcohol is evaporated, a green solid precipitates whichanalysis indicates to be the copper chelate.

Example 6-K The above procedure is used except the cobaltous acetatetetrahydrate is employed to yield a red solid which analysis indicatesto be the cobaltous chelate.

Example 4A C The above procedure is used except that nickelous acetate,Ni(OAC) .4H is employed. A dark green product is formed.

To save repetitive detail, chelates are formed from the above nickel,cobalt and copper salts, and the compounds shown in the following table.

CHELATING AGENTS Compound N-400 N-800 2A N-1200 3A 24-A 4-A 3 1A S-A10-D 3 1 1-0 9..A3 12-01 11-A 5 15-A 3 1 1 4-K1 12O1A 5K1 16"I 1 6 .K117-K2X 9 K1 26A102KA I-Cz 10-U4 2-c 4 3 C2 18A2O2U 5-C 1 4-A C 1 54412-O HUC F LOTATION AGENTS This phase of the invention relates to theuse of the compounds of our invention in separating minerals by frothflotation, and particularly to separating metallic minerals. Theyprovide a novel process for separating minerals or ores into their morevaluable and their less valuable components, by means of a frothflotation operation to beneficiate ores, particularly of metallicminerals, by applying a specifically novel reagent in a froth flotationoperation,

Froth flotation has become established as a highly useful method ofrecovering from ores and minerals the relatively small percentages ofvaluable components they contain. The general technique is to grind theore or mineral to such a degree that the individual grains of thevaluable components are broken free of the less valuable components organgue; make a liquid mass of such finely ground ores, which mass orpulp usually contains a major proportion of water and only a minorproportion of finely-ground ore; subject such pulp to the action of ahighly specific chemical reagent in a flotation machine or flotationcell, in the presence of a large amount of air; and recover the valuableconstituents of the ore from the mineralized froth which overflows fromthe flotation cell. Many variations of this basic procedure have beendeveloped, including the use of different types of filotation cells,different procedures of combining individual operations into differentflow sheets to float successively and separately a number of valuablecomponents, etc. The chemical side of the operation has likewise beenvaried greatly to make such complex operations practicable. In additionto reagents adapted to collect the ore values in the froth (collectors),other reagents for improving the frothing characteristics of theflotation operation (frothers) or for selectively improving or retardingthe flotation of individual members among the valuable components of theore activators or depressors) have been developed. The characteristicsof the chemical reagents that have been used in the flotation operationdiffer greatly, until it may be said that a reagen-ts flotationpossibilities may best be determined by actual test in the process.

Our process relates to the use of the compositions of this invention aspromotors or collectors, particularly in selecting acidic minerals fromother ore constituents. For various reasons, including viscosity, weprefer to employ our reagents in the form of solution in a suitablesolvent. In some instances, where the compounds are water soluble, wateris selected as a solvent. Where the reagent is water insoluble, variousorganic solvents are employed.

We prefer to use our compounds and a solvent in proportions of 1:4 and4:1. In some instances, the best results have been obtained by the useof reagents comprising substantially equal proportions of such twoingredients. 0n the other hand, mixtures in the proportions of 1:9 or911 have sometimes been most useful.

The solvent employed may be selected as desired. In some instances,crude petroleum oil itself is satisfactory; in other cases, gas oil,kerosene, gasoline, or other distillate is to be preferred. We preferspecifically to employ the petroleum distillate sold commercially asstove oil, as it appears to have, in addition to desirable properties asused in our reagent for floating minerals, certain desirable physicalproperties, i.e., it is relatively stable and non-volatile, it isrealtively limpid, and it is relatively nonflammable.

The flotation reagent contemplated for use in our process is prepared bysimply mixing the compound of our invention and the solvent in thedesired proportions. The reagent so compounded is used in the ordinaryoperating procedure of the flotation process.

In some instances, the compounds of the mixture are compatible andcombine into a perfectly homogeneous liquid reagent. In other instances,they are more or less incompatible, and tend to separate or stratifyinto layers on quiescent standing. In instances where the ingredientsare capable of making a homogeneous mixture, the reagent may be handledand used without difliculty. If a non-homogeneous mixtures results whenthe desired proportions are employed, a number of expedients may beresorted to to obviate the difliculty. For example, since it is commonto include the use of -a frothing agent in many flotation operations,the collector which comprises our reagent may be homogenized by beingcombined with a mutual solubilizer in the form of the desired frother,e.g., cresylic acid, pine oil, terpinol, one of the alcoholsmanufactured and used for froth promotion, like the duPont alcoholfrothers, etc. If such mutual solubilizer is incorporated in or with thecompounds and petroleum body, as above described, the resulting reagentis also contemplated by us for use in our process.

Another means of overcoming the non-homogeneity of some of the examplesof the reagents contemplated by us is to homogenize the mixturemechanically, as by a beater or agitator, immediately before injectingit into the mineral pulp which is to be treated for the recovery ofmineral values.

The reagents of the present invention are effective promoters orcollecting agents for acidic ore materials generally and said acidicmaterials may be either worthless gangue or valuable ore constituents.The most important use, however, is in connection with the frothflotation of silica from non-metallic ores in which the siliceous ganguemay represent a much smaller proportion of the ore rather than metallicand sulfide ores in which the gangue usually represents the majorproportion of the ore. Representative acidic ore materials are thefeldspars, quartz, pyroxenes, the spinels, blotite, muscovite, clays,and the like.

Although the present invention is not limited to the treatment of anyparticular ore materials, it has been found to be well suited for frothflotation of silica from phosphate rook, and this is a preferredembodiment of the invention. In the processes of removing silica fromphosphate rock the conditions are such that practically complete removalof the silica must be accomplished in order to produce a salablephosphate material. It is therefore an advantage of this invention thatour reagents not only effect satisfactory removal of the silica but areeconomical in amounts used. For example, the quantities of activecompounds required range from 0.1 pound to 2.0 pounds or more, butpreferably 0.2 to 1.5 pounds, per ton of ore depending upon theparticular ore and the particular reagent. The invention is not,however, limited to the use of such quantities.

These reagents can also be used for the flotation of feldspar fromquartz and for the flotation of mica from quartz and calcite.

The reagents of the present invention can be used alone or in mixtureswith other promoters. They can likewise be used in conjunction withother cooperating materials such as conditioning reagents, activators,frothing reagents, depressing reagents, dispersing reagents, oilymaterials such as hydrocarbon oils, fatty acids or fatty acid esters.

The present reagents are also adaptable for use in any of the ordinaryconcentrating processes such as film flotation, tablin-g, andparticularly in froth flotation operations. The ore concentratingprocesses employed will depend upon the particular type or kind of orewhich is being processed. For example, in connection with phosphate,rock, relatively coarse phosphate-bearing materials, for example 28 meshor larger, can be economically concentrated by using these reagents inconjunction with other materials such as fuel oil or pine oil in aconcentration process employing tables or film flotation. The less than28 mesh phosphate rock material is best concentrated by means of frothflotation employing these improved silica promoters.

When the reagents of the present invention are employed as promoters inthe froth flotation of silica from phosphate rock the conditions may bevaried in accordance with procedures known to those skilled in the art.The reagent can be employed in the form of aqueous solutions, emulsions,mixtures, or solutions in organic solvents such as alcohol and the like.The reagents can be introduced into the ore pulp in the flotation cellwithout prior conditioning or they can be conditioned with the ore pulpprior to the actual concentration operation. They can also be stage fedinto the flotation circuit.

Other improved phosphate flotation features which are known may beutilized in connection with the present invention.

While the above relates specifically to the flotation of silica fromphosphate rock, the present invention is not limited to such operationsand the reagents are useful in the treatment of various other types ofore materials wherein it is desirable to remove acidic minerals in thefroth. For example, the reagents are useful in the treatment of ra kesands from the tailings produced in cement plant operations. In thisparticular instance, the rake sands are treated by flotation to removethe part of the alumina which is present in the form of mica and theremoval of silica is not desirable. Our reagents are useful in suchflotation operations. The reagent may also be used for the flotation ofsilica from iron ores containing magnetite, limonite and quartz, and intests conducted on this type of ore, the rough tailing resulting fromthe flotation of silica containing both magnetite and limonite assayedmuch higher in iron than concentrates produced by the conventional soapflotation of the iron minerals.

Some 10 million tons of phosphate rock are produced annually from theFlorida pebble phosphate deposits. Located principally in Polk andHillsborough Counties, these marine deposits produce three-fourths ofthe US. supply of phosphate and about three-eighths of the world supply.

Such pebble phoshate, as mined by the conventional Strip-mining methods,includes undesirably large proportions of nonaphosphate minerals,principally siliceous and principally silica, which reduce the qualityand the price of this large-tonnage, small-unit-value product. Extensiveand costly ore-dressing plants have consequently been required todeliver a finished product of acceptable grade.

Among the procedures employed, and one which is almost universally usedby the industry, is a two-stage or double flotation process. In thefirst stage (or rougher flotation circuit), washed phosphate rock havingparticle sizes usually between about 28- and about ISO-mesh is subjectedto the action of a reagent conventionally comprising tall oil, fuel oil,and caustic soda. The concentrate delivered by such rougher circuit is aphosphate rock of grade higher than the original rock but which stillcontains too much silica and similar impurities to be of acceptablemarket grade.

The rougher concentrate is therefore dc-oiled with dilute sulfuric acidto remove the tall-oil-soap-and-fuel oil reagent and is thereaftersubjected to flotation in a secondary or cleaner flotation circuit. Thefroth product delivered from this secondary circuit is high in silicaand similar impurities and is desirably low in phosphate values so thatit can be thereafter discarded.

Our process is particularly applicable to such secondary or cleanerflotation circuit of such a conventional flotation scheme. Our processmay, of course, be applied to beneficiate a phosphate rock that has notbeen subjected to such preliminary rougher circuit flotation process.

Because our compounds are most advantageously used in conventionalflotation plants in the phosphate rock industry, and in thesecondary-circuit or cleaner-circuit section of such plants, it is notnecessary here to describe in detail how they are used. Where they areemployed, the operation of the plant is continued in normal fashion, theonly change being the substitution of our compounds for the conventionalreagents otherwise used.

For sake of completeness, the following brief example of their use ispresented.

EXAMPLE A typical Florida pebble phosphat rock is subjected toconventional pre-flotation treatment and sizing. That portion having aparticle-size range of from about 28- to about ISO-mesh is processedthrough a conventional rougher flotation circuit employing theconventional tall oil, fuel oil, and caustic soda reagents to float aphosphate rock concentrate. The concentrate delivered from such roughercircuit contains 1214% insoluble matter, after deoiling with dilutesulfuric acid and washing with water. In the consequent secondaryflotation circuit the compounds of the table below are used at a rate ofabout 085 pound per ton of rougher concentrate.

Aeration is started, additional water being added to the cell asrequired to maintain the proper level as the froth is continuouslyskimmed off. The collected overflow and tailings are analyzed. Theoverflow froth is high in silica and low in bone phosphate of lime whilethe tailing in the underflow are low in silica and high in bonephosphate of lime.

By employing this process with the agents listed below one obtains aphosphate of marketable grade separation of the bone phosphate of limewith these compounds is more efficient than with the conventionalagents.

FLOTATION AGENTS Having thus described our invention, what we claim asnew and desire to obtain by Letters Patent is:

1. A froth flotation process for beneficiating ore containing siliceousmaterials comprising the step of subjecting the ore to froth flotationin the presence of a minor amount, suflicient to effect satisfactoryremoval of the siliceous materials, of a collector selected from thegroup consisting of (1) a branched polyalkylenepolyamine containing atleast three primary amino groups and at least one tertiary amino groupand having the formula at is an integer of 4 to 24, y is an integer of 1to 6, and z is an integer of 0-6, (2) an acylated branchedpolyalkylenepolyamine containing at least three primary amino groups andat least one tertiary amino group and having the formula H NHz R-II) RlINH: y

RNH:

wherein R is an alkylene group having at least two carbon atoms, at isan integer of 4 to 24, y is an integer of l to 6, and z is an integer of0-6, formed by reacting, at a temperature of from about 120 C. to about300 C., said polyalkylenepolyamine with a compound selected from thegroup consisting of (i) a carboxylic acid having 7-39 carbon atoms and(ii) a precursor of said carboxylic acid capable of forming said acid insaid reaction, (3) an oxyalkylated branched polyalkylenepolyaminecontaining at least three primary amino groups and at least one tertiaryamino group and having the x is an integer of 4 to 24,

y is an integer of 1 to 6, and

z is an integer of 0-6, formed by reacting, at a temperature of fromabout C. to about 200 C. and a pressure of from about 10 psi. to about200 psi, said polyalkylenepolyamine with .an alkylene oxide having atleast 2 carbon atoms,

(4) an alkylated branched polyalkylenepolyamine containing at leastthree primary amino groups and 37 at least one tertiary amino group andhaving the formula i EH 1 l N H2 y formula H NHz-( 11-1 1) RN RNHr I i INHs y wherein R is an alkylene group having at least two carbon atoms,

x is an integer of 4 to 24,

y is an integer of 1 to 6, and

z is an integer of -6, formed by reacting, at a temperature of fromabout 70 C. to about 100 C., said polyalkylene polyamine with anolefinating agent selected from the group consisting of acrylonitrile,styrene, butadiene, vinyl ethers and vinyl sulfones,

(6) a Schiff base reaction product of a branched polyalkylenepolyaminecontaining at least three primary amino groups and at least one tertiaryamino group and having the formula x is an integer of 4 to 24,

y is an integer of l to 6, and

z is an integer of 0-6, formed by reacting said polyalkylenepolyaminewith a compound selected from the group consisting of aldehydes andketones,

(7) an acylated, then oxyalkylated branched polyalkylenepolyaminecontaining at least three primary amino groups and at least one tertiaryamino group and having the hereinabove recited formula, formed byreacting, at a temperature of from about 125 C. to about 300 C., saidpolyalkylenepolyamine with an acylating agent selected from the groupconsisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) aprecursor of said carboxylic acid capable of forming said acid in saidreaction, and then reacting said acylated polyalkylenepoly- 38 amine, ata temperature of from about C. to about 200 C. and a pressure of fromabout 10 p.s.i. to about 200 p.s.i., with an alkylene oxide having atleast 2 carbon atoms,

(8) an oxyalkylated, then acylated branched polyalkylenepolyaminecontaining at least three primary amino groups and at least one tertiaryamino group and having the hereinabove recited formula, formed byreacting, at a temperature of from about 80 C. to about 200 C. and apressure of from about 10 p.s.i. to about 200 p.s.i., saidpolyalkylenepolyamine with an alkylene oxide having at least 2 carbonatoms and then reacting said oxyalkylated polyalkylenepolyamine, at atemperature of from about 120 C. to about 300 C., with an acylatingagent selected from the group consisting of (i) a carboxylic acid having7-39 carbon atoms and (ii) is a precursor of said carboxylic acidcapable of forming said acid in said reaction,

(9) an alkylated, then acylated branched polyalkylenepolyaminecontaining at least three primary amino groups and at least one tertiaryamino group and having the hereinabove recited formula, formed byreacting, at a temperature of from about C. to about 250 C., saidpolyalkylenepolyamine with a hydrocarbon halide alkylating agent havingl30 carbon atoms, and then reacting said alkylatedpolyalkylenepolyamine, at a temperature of from about C. to about 300C., with an acylating agent selected from the group consisting of (i) acarboxylic acid having 7-39 carbon atoms and (ii) a precursor of saidcarboxylic acid capable of forming said acid in said reaction,

(10) an acylated, then alkylated branched polyalkylenepolyaminecontaining at least three primary amino groups and at least one tertiaryamino group and having the hereinabove recited formula, formed byreacting at a temperature of from about 120 C. to about 300 C., saidpolyalkylenepolyamine with an acylating agent selected from the groupconsisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) aprecursor of said carboxylic acid capable of forming said acid in saidreaction, and then reacting said acylated polyalkylenepolyamine, at atemperature of from about 100 C. to about 250 C., With a hydrocarbonhalide alkylating agent having 1-30 carbon atoms,

(11) an oxyalkylated, then alkylated branched polyalkylenepolyaminecontaining at least thre primary amino groups and at least one tertiaryamino group and having the hereinabove recited formula, formed byreacting, at a temperature of from about 80 C. to about 200 C. and apressure of from about 10 p.s.i. to about 200 p.s.i., saidpolyalkylenepolyamine with an alkylene oxide having at least 2 carbonatoms, and then reacting said oxyalkylated polyalkylenepolyamine, at atemperature of form about 100 C. to about 250 C., with a hydrocarbonhalide alkylating agent having 130 carbon atoms,

(12) a Schiff base reaction product of an acylated (13) a Schilf basereaction product of an alkylated branched polyalkylenepolyaminecontaining at least three primaryamino groups and at least one tertiaryamino group and having the hereinabove recited formula, formed byreacting at a temperature of from about 100 C. to about 250 C., saidpolyalkylenepolyamine with a hydrocarbon halide alkylating agent havingl-30 carbon atoms, and then reacting said alkylatedpolyalkylenepolyamine with a compound selected from the group consistingof aldehydes and ketones,

(14) an oxyalkylated Schiff base reaction product of a branchedpolyalkylenepolyamine containing at least three primary amino groups andat least one tertiary amino group and having the hereinabove recitedformula, formed by reacting said polyalkylenepolyamine with a compoundselected from the group consisting of aldehydes and ketones to form saidSchiff base reaction product and then reacting said Schiff base reactionproduct, at a temperature of from about 80 C. to about 200 C. and apressure of from about 10 p.s.i., to about 200 p.s.i., with an alkyleneoxide having at least 2 carbon atoms,

(15) an acylated, then olefinated branched polyalkylenepolyaminecontaining at least three primary amino groups and at least one tertiaryamino group and having the hereinabove recited formula, formed byreacting, at a temperature of from about 120 C. to about 300 C., saidpolyalkylenepolyamine with an acylating agent selected from the groupconsisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) aprecursor of said carboxylic acid capable of forming said acid in saidreaction, and then reacting said acylated polyalkylenepolyamine, at atemperature of from about 70 C. to about 100 C., With an olefinatingagent seelcted from the group consisting of acrylonitrile, styrene,butadiene, vinyl ethers and vinyl sulfones, and

(16) an alkylated, then olefinated branched polyalkylenepolyaminecontaining at least three primary amino groups and at least one tertiaryamino group and having the hereinabove recited formula, formed byreacting, at a temperature of from about 100 C. to about 250 C., saidpolyalkylenepolyamine with a hydrocarbon halide alkylating agent havingfrom 1-30 carbon atoms, and then reacting said alkylatedpolyalkylenepolyamine, at a temperature of from about 70 C. to about 100C., with an 01efinating agent selected from the group consisting ofacrylonitrile, styrene, butadiene, vinyl ethers and vinyl sulfones.

2. The process of claim 1 wherein the branched polyalkylenepolyamine isa branched polyethylenepolyamine.

3. The process of claim 1 wherein the branched polyalkylenepolyamine isa branched polypropylenepolyamine.

4. A froth flotation process for removing silica from phosphate rockcomprising the step of subjecting the phosphate rock to froth flotationin the presence of a minor amount, sufficient to effect satisfactoryremoval of the silica from the phosphate rock, of a collector selectedfrom the group consisting of (1) a branched polyalkylenepolyaminecontaining at least three primary amino groups and at least one tertiaryamino group and having the formula x is an integer of 4 to 24, y is aninteger of 1 to 6, and z is an integer of -6,

(2) an acylated branched polyalkylenepolyamine containing at least threeprimary amino groups and at least one tertiary amino group and havingthe formula NH: y

wherein R is an alkylene group having at least two carbon atoms,

(3) an oxyalkylated branched polyalkylenepolyamine containing at leastthree primary amino groups and at least one tertiary amino group andhaving the formula *1 NHz-(R-N) (RN x I 1 NH: y

wherein R is an alkylene group having at least two carbon atoms,

x is an integer of 4 to 24,

y is an integer of 1 to 6, and

z is an integer of 0-6, formed by reacting, at a temperature of fromabout C. to about 200 C. and a pressure of from about 10 p.s.i. to about200 p.s.i., said polyalkylenepolyamine with an alkylene oxide having atleast 2 carbon atoms,

(4) an alkylated branched polyalkylenepolyamine containing at leastthree primary amino groups and at least one tertiary amino group andhaving the formula N Hz-(RN) r N RNH: lit

NH: y

wherein R is an alkylene group having at least two carbon atoms,

x is an integer of 4 to 24,

y is an integer of 1 to 6, and

z is an integer of 0-6, formed by reacting, at -a temperature of fromabout C. to about 250 C., said polyalkylenepolyamine with a hydrocarbonhalide alkylating agent having 1 to 30 carbon atoms,

(5) an olefinated branched polyalkylenepolyamine containing at leastthree primary amino groups and at

1. A FROTH FLOTATION PROCESS FOR BENEFICIATING ORE CONTAINING SILICEOUSMATERIALS COMPRISING THE STEP OF SUBJECT ING THE ORE TO FROTH FLOTATIONIN THE PRESENCE OF A MINOR AMOUNT, SUFFICIENT TO EFFECT SATISFACTORYREMOVAL OF THE SILICEOUS MATERIALS, OF A COLLECTOR SELECTED FROM THEGROUP CONSISTING OF (1) A BRANCHED POLYALKYLENEPOLYAMINE CONTAINING ATLEAST THREE PRIMARY AMINO GROUPS AND AT LEAST ONE TERTIARY AMINO GROUPAND HAVING THE FORMULA